Adsorption of Ions on the Surface of Tin Dioxide and Its Electrokinetic Characteristics in 1 : 1 Electrolyte Solutions

Adsorption and electrokinetic characteristics of tin dioxide (cassiterite) are studied as a function of pH in aqueous NaCl and KCl solutions. The dissociation constants of surface groups, formation constants of ion pairs, and the adsorption potentials of ions are calculated in terms of the 2-pK model; capacities and potentials of the electrical double layer are determined; the dissociation degree of surface groups in the point of zero charge and in the isoelectric point are also estimated. It is shown that the 2-pK model in combination with the Graham model can be applied in the studied systems for describing the experimental results.     

Reversible pH-triggered encapsulation and release of pyrene by adsorbed block copolymer micelles

The well-established ability of copolymer micelles to encapsulate and release hydrophobic molecules has been investigated following their adsorption onto silica particles. Here, a pH-responsive copolymer, poly(2-(dimethylamino)ethyl methacrylate)- b-poly(2-(diethylamino)ethyl methacrylate) (PDMA(106)- b-PDEA(25)), has been used to study the formation and dissociation of adsorbed micelles through pH variation. This copolymer behaves as free unimers in aqueous solutions below pH 8 and forms micelles 29 nm in hydrodynamic diameter above this pH. Encapsulation and release of a model hydrophobic compound (pyrene) by in situ adjustment of the solution pH has been compared for both free and adsorbed micelles using fluorescence spectrophotometry, epifluorescence microscopy, and zeta potential measurements. At basic pH values, pyrene is solubilized within the cores of micelles adsorbed on silica particles: addition of acid leads to micelle dissociation and release of the pyrene into the bulk aqueous solution. Micelle adsorption does not appear to hinder the extent of pyrene uptake/release. Moreover, this pH-responsive behavior is both reversible and reproducible over multiple pH cycles.     

Estimation of the dissociation constants for functional groups on modified and unmodified silica gel supports from the relationship between electroosmotic flow velocity and pH

Electroosmotic volume flow was directly observed in a simple instrument consisting of 1 cm long a home-made support, packed between two polyethylene frits in the polypropylene tube. Equations relating electroosmotic flow (EOF) velocity and pH for two functional groups on the surface of the solid materials were developed. With these equations, we can estimate the dissociation constants of two different kinds of functional groups on modified silica gel materials simultaneously. The dissociation constants of silanol groups, benzene sulfonic acid groups, and alkyl quaternary ammonium groups on the modified and unmodified silica gel supports were estimated. The estimated pK values of the silanol groups on the silica gel and modified silica gel surfaces are between 4.0 and 4.3. The estimated pK values of the benzene sulfonic acid groups and alkyl quaternary ammonium groups on the surface of the modified silica gel are 2.6 and 8.6, respectively.     

Adsorption of codeine on hydrophilic silica and silica surface modified by hydrophobic groups in the presence of electrolytes

The adsorption of codeine from aqueous solution onto colloidal silica and silica surface-modified with chemiadsorbed octadecyl dimethyl silane (ODDMS) or dimethyl silane (DMS) groups was studied in the presence of neutral electrolytes at different pH values. From codeine-hydrochloride solutions codeine cations are strongly bound to negatively charged silica surfaces. Inorganic salts (NaCl, NaNO₃) reduce the adsorption of the organic cation. On silica modified by ODDMS (10% of surface silanol groups are occupied), codeine cations are adsorbed to a higher extent at pH 6, while at pH 8 the adsorbed amounts are lower than on the bare silica surface. Neutral electrolytes reduce codeine adsorption on the ODDMS modified silica. On the hydrophobic silica, completely covered by DMS groups, codeine adsorption is considerably lower than on the bare silica, but neutral salts increase the adsorption. The adsorption of codeine is compared with the adsorption of aggregating surfactant ions. Common and different features of their interactions with silica surfaces are outlined.     

Hydrophobic Effects of o-Phenanthroline and 2,2′-Bipyridine on Adsorption of Metal(II) Ions onto Silica Gel Surface

The effects of o-phenanthroline and 2,2′-bipyridine on the adsorption of metal(II) (Fe, Co, Ni and Cu) ions onto silica gel surface have been studied. The adsorption is expressed in terms of the measured concentrations of both metal and ligand at equilibrium. Each adsorption of the four metal ions is increased with the presence of the ligands. In addition, adsorption increases slowly with pH at low pH values and then increases rapidly up to near the pK_a value of silica gel (≈6.5). The adsorption of each metal ion at low pH is increased with increased ligand concentration. However, at high pH the adsorptions of Fe(II) and Cu(II) are decreased with increased ligand concentration whereas the adsorptions of Co(II) and Ni(II) are always increased. At low pH values the ligand to metal ratio adsorbed on the silica gel surface is ca. 3:1 while at high pH values it is 1:1, 2:1, and 3:1, corresponding to the initial ligand to metal ion concentration ratio. The addition of ethanol to the phenanthroline-SiO₂ solution results in a decrease in the adsorption of phenanthroline. The effect of ethanol is also observed in the Fe(II)-phenanthroline-SiO₂ system. The behavior of the adsorption is interpreted qualitatively by hydrophobic expulsion, the formation of surface complexes, and electrostatic interaction. It is concluded that hydrophobic expulsion plays an important role in the adsorption of metal ions in the presence of hydrophobic ligands on silica gel surface.     

Removal of uranium(VI) and thorium(IV) ions from aqueous solutions by functionalized silica: kinetic and thermodynamic studies

Adsorption behavior of uranyl and thorium ions from synthetic radioactive solutions onto functionalized silica as sorbent has been investigated. The effect of contact time, initial concentration of radioactive solutions, sorbent mass, pH value and temperature on the adsorption capacity of the sorbent was investigated. Negative values of Gibbs free energy of adsorption suggested the spontaneity of the adsorption process on both functionalized silica with –NH₂ groups and with –SH groups. Positive values obtained for ΔH° indicates that the adsorption is an endothermic process. The adsorption isotherms were better fitted by Freundlich model and the adsorption kinetic was well described by the pseudo-second order equation. Desorption studies indicated that the most favorable desorptive reagents for UO₂ ²⁺ is HNO₃ 1 M and for Th⁴⁺ is EDTA 1 M solutions.     

Ternary surface complexes in silica-Ni2+ ions-2,2′-dipyridyl systems

The adsorption of complexes of nickel ions with an organic base (2,2′-dipyridyl) at an interface between silica and an aqueous electrolyte solution has been considered in terms of the theory of complexation. It has been shown that, on the silica surface, ternary complexes are formed, in which nickel ions are bonded to silanol groups. The equilibrium constants of the reactions of ternary surface complex formation have been calculated from the adsorption curves describing the pH dependences of nickel ion and dipyridyl adsorption.     

Background electrolytes in 50% methanol/water for the determination of acidity constants of basic drugs by capillary zone electrophoresis

The acidic dissociation constants of several hydrophobic drugs, amiodarone and a series of antidepressants that show a secondary or tertiary amino group, were determined in a 50% methanol/water mixture by capillary zone electrophoresis. The electrophoretic behavior of buffers prepared from sodium acetate, tris(hydroxymethyl) aminomethane hydrochloride, sodium hydrogenphosphate, ammonium chloride, ethanolamine, butilammonium chloride, and sodium borate in the hydroalcoholic solution was tested. Thus, all of them follow the Ohm's law until about 25 kV and, therefore, they can be used without significant Joule heat dissipation at 20 kV. For the studied drugs, buffers prepared with phosphate or borate give effective mobility measurements lower than those from other buffers. The wide pKa range of the studied drugs provides a wide pH range where the protonated forms of the amino compounds coexist with hydrogenphosphate ions and where the neutral amines coexist with boric acid. The decrease of the experimental effective mobilities in these instances can be explained through the interactions between coexisting species. Therefore, phosphate and borate buffers should be avoided to determine the mobility of amines with aqueous pKa higher than 8, at least in solutions with high methanol content. Independent measurements of acidic dissociation constants of drugs validate this statement.     

Influence of the solute hydrophobicity on the enantioselective adsorption of beta-blockers on a cellulase protein used as the chiral selector

Adsorption isotherm data were acquired at different eluent pH values for the enantiomers of several beta-blockers on cellobiohydrolase I on silica gel. They fit well to the biLangmuir model, allowing the determination of the equilibrium constants and the monolayer capacities for chiral and nonselective adsorption. The adsorption of the S-enantiomers (eluted second) is exothermic at low pH, endothermic at high pH, and athermal in a narrow pH range depending on the beta-blocker. This transition pH range is lower for S-alprenolol than for the more hydrophobic S-propranolol, although their endothermic adsorption originates from hydrophobic interactions. This surprising observation is explained by the relative values of the isotherm coefficients. S-Alprenolol seems to have a more pronounced endothermic behavior than S-propranolol because the nonselective interactions of both compounds with the stationary phase are exothermic but their contribution to retention, relative to that of the endothermic chiral interactions, is less important for alprenolol. The order of increasing energy of the chiral interactions is the same as that of hydrophobicity, propranolol>alprenolol>metoprolol.     

Free energies of protein adsorption onto mineral particles — from the initial encounter to the onset of hysteresis

The kinetics and energetics of human serum albumin (HSA) adsorption onto silica and talc particles are compared, from the earliest moment of contact, up to 24 h exposure. The measured affinity constants are used to obtain the free energies of interaction (ΔG). The free energies of interaction are also obtained via the measured surface properties of HSA, water, silica and talc. Comparison between the ΔG-values obtained by the two different approaches makes it possible to deduct the manner and conformation of HSA adsorption at the earliest moment, as well as after onset of hysteresis. Two different modes of hysteresis are identified — one allows slow dissociation and the other approaches apparent irreversibility. The mechanisms of both are elucidated, as is the mechanism of desorption at high pH and by displacement with identical or quasi-identical molecules.     

表面印迹法制备钴(Ⅱ)离子印迹硅胶及性能

采用表面印迹技术, 以Co(Ⅱ)离子作为印迹离子, 二乙烯三胺基丙基三甲氧基硅烷为功能分子, 硅胶为支撑物, 环氧氯丙烷为交联剂, 在硅胶表面制备Co(Ⅱ)离子印迹硅胶材料, 利用红外光谱仪、扫描电镜和热重分析仪等进行了表征, 采用平衡吸附法研究了印迹硅胶材料的吸附性能和选择识别能力. 结果表明, 印迹硅胶材料和非印迹硅胶材料的最大吸附量分别为35.2和6.5 mg/g; 印迹硅胶材料对Co(Ⅱ)离子的吸附行为符合Langmuir模型; 20 min即可达到吸附平衡; 当pH=3.9~7.8时, 印迹硅胶材料保持了较好的吸附容量; 印迹硅胶材料对Co(Ⅱ)离子具有较强的选择性识别能力; 重复使用时性能稳定.     

Kinetic modeling of ion conduction in KcsA potassium channel

KcsA constitutes a potassium channel of known structure that shows both high conduction rates and selectivity among monovalent cations. A kinetic model for ion conduction through this channel that assumes rapid ion transport within the filter has recently been presented by Nelson. In a recent, brief communication, we used the model to provide preliminary explanations to the experimental current-voltage J-V and conductance-concentration g-S curves obtained for a series of monovalent ions (K(+),Tl(+), and Rb(+)). We did not assume rapid ion transport in the calculations, since ion transport within the selectivity filter could be rate limiting for ions other than native K(+). This previous work is now significantly extended to the following experimental problems. First, the outward rectification of the J-V curves in K(+) symmetrical solutions is analyzed using a generalized kinetic model. Second, the J-V and g-S curves for NH(4) (+) are obtained and compared with those of other ions (the NH(4) (+) J-V curve is qualitatively different from those of Rb(+) and Tl(+)). Third, the effects of Na(+) block on K(+) and Rb(+) currents through single KcsA channels are studied and the different blocking behavior is related to the values of the translocation rate constants characteristic of ion transport within the filter. Finally, the significantly decreased K(+) conductance caused by mutation of the wild-type channel is also explained in terms of this rate constant. In order to keep the number of model parameters to a minimum, we do not allow the electrical distance (an empirical parameter of kinetic models that controls the exponential voltage dependence of the dissociation rate) to vary with the ionic species. Without introducing the relatively high number of adjustable parameters of more comprehensive site-based models, we show that ion association to the filter is rate controlling at low concentrations, but ion dissociation from the filter and ion transport within the filter could limit conduction at high concentration. Although some experimental data from other authors were included to allow qualitative comparison with model calculations, the absolute values of the effective rate constants obtained are only tentative. However, the relative changes in these constants needed to explain qualitatively the experiments should be of significance.     

One-pot preparation of silica-supported hybrid immobilized metal affinity adsorbent with macroporous surface based on surface imprinting coating technique combined with polysaccharide incorporated sol--gel process

A simple and reliable one-pot approach using surface imprinting coating technique combined with polysaccharide incorporated sol-gel process was established to synthesize a new organic-inorganic hybrid matrix possessing macroporous surface and functional ligand. Using mesoporous silica gel being a support, immobilized metal affinity adsorbent with a macroporous shell/mesoporous core structure was obtained after metal ion loading. In the prepared matrix, covalently bonded coating and morphology manipulation on silica gel was achieved by using one-pot sol-gel process starting from an inorganic precursor, -glycidoxypropyltrimethoxysiloxane (GPTMS), and a functional biopolymer, chitosan (CS) at the atmosphere of imprinting polyethylene glycol (PEG). Self-hydrolysis of GPTMS, self-condensation, and co-condensation of silanol groups (Si-OH) from siloxane and silica gel surface, and in situ covalent cross-linking of CS created an orderly coating on silica gel surface. PEG extraction using hot ammonium hydroxide solution gave a chemically and mechanically stabilized pore structure and deactivated residual epoxy groups. The prepared matrix was characterized by using X-ray energy dispersion spectroscopy (EDX), scanning electron microscopy (SEM) and mercury intrusion porosimetry. The matrix possessed a high capacity for copper ion loading. Protein adsorption performance of the new immobilized metal affinity adsorbent was evaluated by batch adsorption and column chromatographic experiment using bovine serum albumin (BSA) as a simple model protein. Under the optimized coating conditions, the obtained macroporous surface resulted in a fast kinetics and high capability for protein adsorption, while the matrix non-charged with metal ions offered a low non-specific adsorption.     

Fragment ion formation of quaternary ammonium salts under fast atom bombardment and field desorption collisionally activated dissociation conditions

Comparing fast atom bombardment and field desorption collisionally activated dissociation mass spectra of tetrabutyl ammonium salts it becomes evident that under fast atom bombardment conditions, besides desorption of intact salt cations, the ionization of intact salt molecules must be assumed. Alkyl ions formed under fast atom bombardment and not under field desorption collisionally activated dissociation conditions are ionization products of tetraalkyl ammonium salt molecules. Radical cations are produced by both techniques.     

Effect of the steric accessibility of the exchange site in long-chain quaternary ammonium salts on the anion-exchange extraction of divalent ions

The constants of anion-exchange extraction of divalent ions by quaternary ammonium salts of various structures were determined. The exchange constants depend significantly on steric accessibility of the exchange site. For the exchange of small-size anions, the affinity of the ion exchanger for divalent ions is higher than for monovalent ions. For large divalent anions, the exchange constant may increase or decrease, depending on the size of a monovalent anion. The obtained results are explained by the specifics of the ion-pair association of monovalent and divalent anions with quaternary ammonium cations.     

玻璃硅烷化处理对罗丹明6G和亚甲基蓝吸附行为的影响

利用六甲基二硅烷胺对平面玻璃光波导(高折射率透明导光薄膜介质)进行硅烷化处理, 得到水接触角大于90°的疏水表面. 然后使用时间分辨光波导分光光谱技术研究水溶液中的罗丹明6G (R6G)和亚甲基蓝(MB)分子在疏水玻璃表面的吸附行为, 并与亲水玻璃条件下测得的结果进行对比. 对利用疏水玻璃光波导测得的R6G的吸附-脱附动力学曲线进行Langmuir拟合得到了R6G的吸附速率常数, 脱附速率常数以及吸附自由能. 并且发现与亲水玻璃情况相比, 吸附速率常数增大, 脱附速率常数减小, 吸附自由能更负. 在疏水玻璃表面形成的R6G和MB吸附层的吸光度与亲水玻璃情况相比显著升高, 表明这两种分子更倾向于吸附在疏水玻璃表面. 实验结果还发现玻璃硅烷化处理能够有效抑制这两种染料分子在表面的聚合反应.     

Synthesis of novel ion‐imprinted polymeric nanoparticles based on dibenzo‐21‐crown‐7 for the selective pre‐concentration and recognition of rubidium ions

In this work, we report the first application of ion‐imprinted technology via precipitation polymerization for simple and practical determination of rubidium ions. The rubidium‐ion‐imprinted polymer nanoparticles were prepared using dibenzo‐21‐crown‐7 as a selective ligand, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross linker, and 2,2′‐azobisisobutyronitrile as radical initiator. The resulting powder material was characterized using scanning electron microscopy, which showed colloidal nanoparticles of 100–200 nm in diameter and slightly irregular in shape. The maximum adsorption capacity of the ion imprinted particles was 63.36 μmol/g. The experimental conditions such as nature and concentration of eluent, pH, adsorption and desorption times, weight of the polymer material, aqueous phase and desorption agent volumes were also studied. Finally, selectivity of the prepared IIP particles toward rubidium ion was investigated in the presence of some foreign metal ions.     

The Effect of Specific Adsorption of Cations and Their Size on the Charge‐Compensation Mechanism in Carbon Micropores: The Role of Anion Desorption

Combined application of cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM) technique reveals a complicated interplay between the adsorption of ammonium and lower molecular weight tetraalkyl ammonium cations and desorption of Cl^? anions inside carbon micropores at low surface charge densities, which results in failure of their permselectivity. Higher negative surface charge densities induce complete exclusion (desorption) of the Cl^? co‐ions, which imparts purely permselective behavior on the carbon micropores. The second fundamental effect discovered herein relates to the dominant role of anion desorption (as compared to cation adsorption), that is, overwhelming failure of permselectivity extends to high negative charge densities of the electrode in the presence of bulky tetraalkyl ammonium cations, which tend to be confined in the micropores of the carbon. The results obtained are important for advancement of high power density carbon‐based supercapacitors, nanofiltration technologies with porous carbon membranes, and studies of ionic transport across biological membranes.     

Indirect detection in reversed-phase liquid chromatography: Ion-pair retention models for cations on polystyrene polymers

Summary The distribution equilibria of cationic compounds in reversed-phase chromatographic systems (ion-pair chromatography) have been studied on the basis of their effect on a detectable mobile phase component. The solid phase was a polystyrene-divinylbenzene copolymer and the detectable component, a quaternary ammonium ion, 1-methylpyridine. The solutes were mono- and divalent amines and quaternary ammonium ions. The cations can be retained by ion-pair adsorption and ion exchange. Expressions for the ion-pair retention of the solutes and the mobile phase cation (system peak) have been developed assuming Langmuir distribution of ion pairs to a solid phase with one kind of binding site. The validity of the expressions has been tested by evaluation of ion-pair distribution constants using non-linear curve fitting techniques. Good agreement for the constants of common ion pairs was obtained from different kinds of capacity ratio expressions. Ion exchange retention can appear beside ion-pair retention, and it has been observed in the pH range 1.6–6.1. The effect depends not only on cations in the mobile phase, but also on the nature of the buffering systems.     

Exponential sensitivity and speciation of Al(III), Sc(III), Y(III), La(III), and Gd(III) at fused silica/water interfaces

The binding contants, adsorption free energies, absolute adsorbate number densities, and interfacial charge densities of Al(III), Sc(III), Y(III), La(III), and Gd(III) interacting with fused silica/water interfaces held at pH 4 were determined using second harmonic generation and the Eisenthal χ((3)) technique. By examining the relationship between the measured adsorption free energies and the electric double layer interfacial potential at multiple electrolyte concentrations, we elucidate the charge state and possible binding pathways for each ion at the fused silica surface. Al(III) and Sc(III) ions are found to bind to the fused silica surface as fully hydrated trivalent species in a bidentate geometry. In contrast, the Y(III), La(III), and Gd(III) ions are each shown to adsorb to the silica surface in a decreased charge state, but the extent and mode of binding varies with each ion. By quantifying the exponential sensitivity of the surface coverage of the adsorbed ions to their charge state directly at the fused silica/water interface, we provide benchmarks for theory calculations describing the interactions of metal ions with oxide interfaces in geochemistry and hope to improve the prediction of trivalent metal ion transport through groundwater environments.